Transition metal crosslinking of acid-containing polymers

ABSTRACT

Acid-functional polymer is reacted with a transition metal compound at a temperature above the T g  of the polymer to produce crosslinked polymer. The process produces a liquid polymer product that dries to a crosslinked film without the required presence of volatile ligands. Improved coating such as floor polishes are also disclosed.

This is a divisional Ser. No. 690,375, filed Apr. 23, 1991, now U.S.Pat. No. 5,149,745

BACKGROUND OF THE INVENTION

It has been known in the art to add stable complex salts of transitionmetals such as zinc to emulsions and dispersions of acid containingpolymers, (U.S. Pat. Nos. 3,308,078, 3,328,325, 3,467,610, 3,554,790,4,150,005, and 4,517,330, ).

In practicing this chemistry, complex salts are formed from simple saltor oxides of transition metals with amines or other simple complexingligands. (In the following formulae `M` indicates a transition metal,`L` indicates a ligand). ##STR1##

Since each of the above steps in the formation of the complex from thefree (or hydrated) metal ion is reversible and runs to equilibrium, theprocess must be forced to completion (tetradentate ligand complex) bymass action, charging an excess of the ligand species. The complexingagent must be a simple ligand, to avoid the formation of very stablecomplex structures that will not donate metals to the acidic polymer.

The metal complex is formed before addition to the polymer to increasethe ion complex surface area, decreasing the charge per unit area, sothat the acid containing polymer is stable in the presence of themultivalent ion. The instability of acid containing polymers tomultivalent ions is well known and, in fact, they be are commonly usedto flocculate and precipitate polymers from waste streams (Fe++, Fe+++and AI+++ salts are most commonly used). The reduced charge density ofthe complex multivalent salt provides only minimal disruption of thepolar double layer thought to be responsible for polymer emulsionstability.

When the complex salt solution is added to the acidic emulsion polymer,the salt undergoes counterion exchange. Most commonly, the complexmultivalent cations are prepared as carbonate, bicarbonate, or acetatesalts. As this technology is generally understood, the only limitationof the anion of the salt is that it be a stronger base than the anion ofthe pendant polymeric acid. If weaker base anions, such as chloride,etc., are used as the salt, crosslinking apparently does not occurbecause the process of counterion exchange does not happen; the weakerbase anions do not displace the anion of the polymeric acid. (In thefollowing ##STR2## represents an acid functional group attached to apolymer). ##STR3##

The conjugate acid of the anion of the stable metal complex must beeither volatile or unstable. For instance, acetic acid, the conjugateacid of acetate anion, is volatile, and carbonic acid, the conjugateacid of both bicarbonate and carbonate anions, is unstable(spontaneously decomposing to carbon dioxide and water). In practice,the evolution of volatile conjugate acid, or the volatile by-products ofthe decomposition of the unstable conjugate acid is a processing problemencountered duringthis crosslinking reaction.

The complex cation, in close association with polymer carboxylate anionsprovides latent crosslinking of the polymer (Maintenance ChemicalSpecialties, by Walter J. Hackett. Chemical Publishing Co., Inc. N.Y.,1972. pp9-13. ). This crosslinking has been referred to as latentbecause it occurs only after the volatile (amine) ligand is releasedfrom the metal during the polymer film formation stages. ##STR4##

The latent crosslinking may be due to the formation of insolublemetal-polymeric carboxylate salts, or the formation of polymericcarboxyl complexes with the metals. ##STR5##

Complexed transition metal salt latent crosslinking has thus enabled theart to produce polymers that will crosslink in a coating upon drying,without interfering with the film formation process. Since the finalcrosslinked polymer effectively has the pendant acid functionality tiedup in insoluble acid-metal salts or complexes, metal crosslinkedpolymers have improved resistance to alkaline materials, such asdetergents or cleaning solutions.

The addition of low levels (typically 1 to 3%) of ammonia or other amineto a cleaner solution is believed to effectively reverse thecrosslinking process. The free metal-amine complex is re-formed, thusfreeing the polymeric acid functionality which may then be attacked bysimple alkaline materials. These amine-containing cleaner solutions areknown as strippers, since they effectively allow for the removal of thepreviously crosslinked films.

One problem of this chemistry has been that application of multiplecoats of compositions containing these metal salt complexes cansometimes prove difficult because the new wet coat of polymercomposition contains a high concentration of the complexing amineliqand. This high concentration of free amine, and the amine ligandreleased from the complex, act as a stripper on the previously appliedunder-coat causing redispersion of the under-coat, drag in theapplication of the top coat, whitening and ghosting of the coating, andgeneral disruption of the recoating process known as poor recoatability.These difficulties are particularly noted when coating formulations areapplied rapidly, as is common practice in industrial applications.

Though transition metal salt latent crosslinking of acid-containingemulsion polymers has provided many improvements in dry film properties,the high ammonia content of transition metal complex formulations isdisadvantageous in that it is mildly toxic and highly odoriferous. Thevolatile ligands lead to difficulties in handling, formulating, and useof the emulsion polymers produced by this technology.

OBJECTS OF THE INVENTION

An object of the invention is to provide a composition that produces afilm that exhibits a balance of detergent resistance and removability.

Another object is to provide such a composition that does not generatean objectionable odor, such as that of ammonia, on drying.

A further object is to provide a composition that can be rapidlyrecoated without degrading earlier applied coats of the composition.

SUMMARY OF THE INVENTION

An acid-functional polymer is reacted with a transition metal compoundat a temperature above the glass transition temperature (T_(g)) of thepolymer. The transition metal compound is maintained in contact with thepolymer for a time sufficient to allow the reaction to occur.

The films produced from the polymer compositions produced according tothe invention exhibit the advantages of the crosslinked, detergentresistant films produced through latent metal salt crosslinking withoutthe toxicity, odor, or application problems associated with the use ofvolatile ligands, such as amines, that have previously been employed incrosslinking acid-containing polymers. Moreover, the process of theinvention appears to produce a more complete crosslinking of the acidfunctionality of the polymer than latent metal salt crosslinking asindicated by the ability to produce higher stoichiometric levels ofreaction with the acid functionality of the polymer when practicing theinvention.

DETAILED DESCRIPTION OF THE INVENTION I . POLYMERS

Polymeric materials must meet two criteria to be useful in thisinvention. They must be dissolved or dispersed in water and must containpendant acid functionality. Polymers that contain acid functionalityonly as termini or end groups do not produce the desired crosslinkedpolymer and film properties.

The acid functionality may be incorporated in the polymer by known meansusing an effective amount, preferably from 4 to 90% by weight of thetotal monomers of acidic monomers. Examples of acidic monomers areethylenically unsaturated acid monomers, such as acrylic acid,methacrylic acid, maleic acid, itaconic acid, maleic anhydride, vinylphenol and mixtures thereof.

Other monomers in the polymer preparation are selected to produce thedesired end use and application properties sought and include thepolymerizable comonomers which form soft polymers in the presence offree radical catalysts and those that produce hard polymers in thepresence of free radical catalysts. Examples of comonomers whichpolymerize to form soft polymers include primary and secondary alkylacrylate, with alkyl substituents up to eighteen or more carbon atoms,primary or secondary alkyl methacrylates with alkyl substituents of fiveto eighteen or more carbon atoms, or other ethylenically-unsaturatedcompounds which are polymerizable with free radical catalysts to formsoft solid polymers, including vinyl esters of saturated monocarboxylicacids of more than two carbon atoms. The preferred ethylenicallyunsaturated compounds are the stated acrylates, itaconates, andmethacrylates, and of these the most preferred esters are those withalkyl groups of not more than 8 carbon atoms.

The preferred monomers which by themselves yield soft polymers may besummarized by the formula ##STR6## wherein R' is hydrogen or a methylgroup and, when R' is methyl R^(x) represents a primary or secondaryalkyl group of 5 to 18 carbon atoms, and when R' is hydrogen, R^(x)represents an alkyl group of not over 18 carbon atoms, preferably of 2to 8 carbon atoms and more preferably 2 to 4 carbon atoms.

Typical compounds coming within the above definition are ethyl acrylate,proply acrylate, isoproply acrylate, butyl acrylate, isobutyl acrylate,sec-butyl acrylate, amyl acrylate, isoamyl acrylate, hexyl acrylate,2-ethylhexyl acrylate, octyl acrylate, 3,5,5-trimethylhexylacrylate,decyl acrylate, dodecyl acrylate, cetyl acrylate, octadecyl acrylate,octadecenyl acrylate, n-amyl methacrylate, sec-amyl methacrylate, hexylmethacrylate, 2-ethylhexyl methacrylate, 2-ethylbutyl methacrylate,octyl methacrylate, 3,5,5-trimethylhexyl methacrylate, decylmethacrylate, dodecyl methacrylate, octadecyl methacrylate, and thosewith substituted alkyl groups such as butoxylethyl acrylate ormethacrylate.

Another group of monomers which by themselves yield soft polymers arebutadiene, chloroprene, isobutene, and isoprene. These are monomerscommonly used in rubber latices along with a hard monomer also useful inthis invention, such as acrylonitrile, styrene, and other hard monomersas given above. The olefin monomers, particularly ethylene andpropylene, are also suitable soft monomers.

Examples of polymerizable ethylenically unsaturated monomers which bythemselves form hard polymers, are alkyl methacrylates having alkylgroups of not more than four carbon atoms and alkyl acrylates havingalkyl groups of not more than 2 carbon atoms also tert-amylmethacrylate, ter-butyl or tert-amyl acrylate, cyclohexyl, benzyl orisobornyl acrylate or methacrylate, acrylonitrile, or methacrylonitrile,these constituting a preferred group of the compounds forming hardpolymers. Styrene, vinyl chloride, chloride, chlorostyrene, vinylacetate and a-methylstyrene, which also form hard polymers, may be used.

Preferred monomers, which by themselves form hard polymers, may besummarized by the formula ##STR7## wherein R' is hydrogen or a methylgroup and wherein X represents one of the groups --CN, phenyl,methylphenyl, and ester-forming groups, --COOR", wherein R" iscyclohexyl or methyl or ethyl or a tert-alkyl group of four to fivecarbon atoms, or, when R' is methyl, an alkyl group of two to fourcarbon atoms. Some typical examples of these have already been named.Other specific compounds are methyl methacrylate, ethyl methacrylate,propyl methacrylate, isoproply methacrylate, isobutyl methacrylate,n-butyl methacrylate, sec-butyl methacrylate, and tert-butylmethacrylate. Acrylamide and methacrylamide may also be used ashardening components of the copolymer.

A further class of polymers of this invention are polymers of the estersof vinyl alcohol such as vinyl formate, vinyl acetate, vinyl propionate,vinyl butyrate and vinyl versitate. Preferred is poly(vinyl acetate) andcopolymers of vinyl acetate with one or more of the following monomers:vinyl chloride, vinylidene chloride, styrene, vinyl toluene,acrylonitrile, methacrylonitrile, acrylate or methacrylate esters, andthe functional group containing monomers given above.

These polymers can be prepared, for example by emulsion copolymerizationof the several monomers in the proper proportions. Conventional emulsionpolymerization techniques are described in U.S. Pat. Nos. 2,754,280 and2,795,564. Thus the monomers may be emulsified with an anionic, acationic, or a nonionic dispersing agent, about 0.5% to 10% thereofbeing used on the weight of total monomers. When water-soluble monomersare used, the dispersing agent serves to emulsify the other, lesssoluble monomers. A polymerization initiator of the free radical type,such as ammonium or potassium persulfate, may be used alone or inconjunction with an accelerator, such as potassium metabisulfite, orsodium thiosulfate. The initiator and accelerator, commonly referred toas catalyst, may be used in proportions of 1/2 to 2% each based on theweight of monomers to be copolymerized. The polymerization temperaturemay be from room temperature to 90° C. or more as is conventional.

Examples of emulsifiers or soaps suited to this polymerization processinclude alkali metal and ammonium salts of alkyl, aryl, alkaryl, andaralkyl sulfonates, sulfates, and polyether sulfates; the correspondingphosphates and phosphonates; and ethoxylated fatty acids, alcohols,amines, amides, and alkyl phenols.

Chain transfer agents, including mercaptans, polymercaptans, andpolyhalogen compounds, are often desirable in the polymerization mix.

Staged or sequential copolymers can also be crosslinked according to theinvention. Particularly useful first stage copolymers areethylene/ethylacrylate copolymers and ethylene/vinyl acetate copolymerscontaining added hydrophilic monomer.

Unless otherwise indicated, "T_(g) " indicates the calculated glasstransition temperature according to the method of T.G. Fox, Bull. Am.Phys. Soc. 1 (3), 123 (1956).

Metals

All of the transition metals are capable of forming polymericcrosslinks, though care must be exercised when considering the use ofarsenic, mercury, cobalt, copper, lead, cadmium, nickel and chromium fora specific application due to high cost, toxicity, or the production ofa color in the polymeric film. Certain transition metals such asaluminum, tungsten, and tin that could not be used in latent metal saltcrosslinking because of their inability to form a stable amine complex,are useful in the present invention. Combinations of transition metalsmay be effectively used. The divalent alkaline metals are generally noteffective as crosslinking agents.

The preferred metals, based on criteria of low cost, low toxicity, andlow color in the crosslinked film, include zinc, aluminum, tin, tungstenand zirconium. Zinc and aluminum are particularly preferred. Usefulcompounds of the transition metals include the oxide, hydroxide,carbonate and acetate (usually the basic acetate due to the solubilityconcern discussed below).

When used in emulsion or dispersions of acid-containing polymer, themetal compounds must be relatively insoluble since even moderatelysoluble salts (i.e. ≧0.4% in water at 60° C.) can produce excessivelyhigh levels of multivalent cations in solution. High levels ofmultivalent cations can cause dispersions or emulsions ofacid-containing polymer to precipitate or sediment from the dispersionor emulsion because of the polymer's multivalent cation instability (thedouble layer is believed to be disrupted by multivalent cations). Thisrequirement for a low solubility transition metal compound does notapply to acid-containing polymers in aqueous solution, but only toaqueous dispersions and emulsions of acid-containing polymers.

REACTION WITH TRANSITION METAL COMPOUND

In one embodiment, the process of the invention is practiced by charginga reaction zone with an acid-containing polymer in dispersion orsolution, and charging to this, while the polymer is maintained at atemperature above its effective glass transition temperature (Tg), anappropriate amount of transition metal compound. The compound ismaintained in contact with the acid-containing polymer, at the elevatedtemperature, until the reaction is completed. The point of completion ofthe reaction is indicated by an observable reduction in opacity and anincrease in the pH of the reaction mixture. The process can also bepracticed by heating the polymer dispersion after the insoluble metalcompound has been added. The reaction zone can be any suitable reactionvessel or area in a reactor. The transfer of materials from one vesselor portion of a reactor, if performed during the reaction, will bringthe additional vessel or area under the team reaction zone. The processmay be practiced as a batch, continuous or semi-continuous process.

The maximum amount of transition metal compound for use in dispersion oremulsion system can be determined by reference to the amount(equivalence) of pendant acid functionally in the polymer and thenselecting the desired amount of metal based on the known valence of themetal ion. Divalent metal ions will stoichiometrically react with twoequivalents of acid per mole of metal salt, and trivalent metal ionswill react with three equivalents of acid. Monovalent metal salts willnot effectively crosslink the polymer by this technique.

It is generally desireable to use less than a full stoichiometricequivalent of the metal to reduce the chance of accidentally chargingmore of the metal than the reaction will consume. The presence of anunreacted excess could decrease the emulsion stability or produce aresidue of metal compound in the resulting film which is undesired insome uses of the reaction product.

If the metal compound is added in finely divided form the reaction willproceed more rapidly. Pre-dispersing the finely divided metal compoundwill produce an even more rapid reaction. Generally the extent oreffectiveness of the reaction is not changed by these modifications,only the speed of the reaction. If the acid-containing polymer isprepared as an aqueous solution polymer with moderate to low solubilityit is necessary that the insoluble metal compound be added as a veryfine powder or aqueous dispersion. Failure to follow this caveat withlow solubility aqueous solution polymers can result in the particles ofmetal compound being coated with a layer of insoluble polymeric metalsalt which will effectively retard further reaction of the polymer withthe transition metal compound.

Water insoluble acid-containing polymer dispersions must be maintainedin the acid form before addition of the insoluble metal compound.Partial neutralization of the polymer (2-20%) may be carried out toimpart polymer emulsion stability or polymer solubility, but moreextensive neutralization (for example ≧50%) retards the speed of thereaction of polymer with metal compound.

Water soluble acid-containing polymers must be neutralized to an extentsufficient to maintain their water solubility during reaction with themetal compounds. Polymers of low solubility will require a higher degreeof neutralization to maintain solubility during the reaction, and thoseof higher solubility will require a lesser degree of neutralization.However, the higher the degree of neutralization of the polymeric acidfunctionality, the slower will be the reaction with the transition metalcompound.

In some uses of the polymer product of the invention, such as floorpolish vehicles, it is necessary that the polymer emulsion have a pHgreater than 7.0 so that it will allow other formulation ingredients,such as anionic fluorocarbon surfactant wetting agents, to function intheir intended manner. It is preferred that this pH adjustment be madeafter the polymer emulsion has been reacted with the insoluble metalcompound so that the majority of the polymeric acid functionalityremains in the acid form and the rate of the reaction is notsignificantly slowed. In some applications of emulsion polymer productit is desirable to neutralize the polymer or formulation with a volatilebase, such as ammonia or other amine. It is preferred that any suchbasification be carried out after the polymer has been reacted with theinsoluble transition metal compound. The invention can provide morehighly crosslinked polymers and formulations which are stabilized byneutralization with base but exhibit a much lower pH than is possiblewith amine-complex crosslinking. The mixed metal crosslinking technologydisclosed in U.S. Pat. No. 4,517,330 may be practiced along with theprocess of the invention. It is most desirable to practice thistechnology by adding the basic alkali metal salt after the polymer hasbeen reacted with the transition metal compound, in order to provideacceptible reaction rates. A fraction of the basic alkaline metal saltmay be used to prebasify a small percentage of the polymeric acidfunctionality to provide enhanced polymer stability during the reaction,as has been described above.

The polymer products of the invention are suitable for any uses in whicha polymer having a T_(g) above room temperature are useful and areparticularly suited to uses that must exhibit resistance to chemical orphysical challenges. These uses include coatings such as paints,polishes, particularly floor polishes, industrial and maintenancecoatings.

The following examples are provided to further illustrate the practiceof aspects of the invention. These examples should not be read aslimiting the scope of the invention which is described in thespecification and claims. Unless otherwise stated parts are parts byweight and percentages are percentages by weight.

POLYMER PREPARATION Monomer mixture preparation

An emulsified monomer mixture is prepared by slowly adding the followingmonomers in sequence to a stirred solution of 77 grams of a 28% solutionof sodium lauryl sulfate (SLS) in 2600 grams of deionized water:

    ______________________________________                                                        weight    (percent by weight                                  monomer         (grams)   of total monomer)                                   ______________________________________                                        butyl acrylate (BA)                                                                           1981      (28%)                                               methyl methacrylate (MMA)                                                                     4387      (62%)                                               methacrylic acid (MAA)                                                                         707      (10%)                                               ______________________________________                                    

Procedure A

In a suitable reaction vessel equipped with a thermometer, condensor,and stirrer, a solution of 176 grams of 28% SLS solution and 5150 gramsdeionized water is heated to 80°-85° C. A 164 gram portion of themonomer emulsion described above is added all at once to the reactionvessel and the temperature adjusted to 80°-82° C. The kettle chargeammonium persulfate (APS) catalyst solution (41.5 grams dissolved in 200grams water) is added all at one. Within above five minutes the onset ofpolymerization is signalled by a temperature rise of 3°-5° C. and achange in the appearance (color and opacity) of the reaction mixture.When the exotherm has ceased, the remaining monomer mixture and thecofeed catalyst solution (20.7 grams APS in 600 grams deionized water)are gradually added to the reaction vessel. The rate of addition must bechosen based on the rate at which the heat of the polymerizationreaction can be removed by cooling (2-3 hrs). The polymerizationreaction temperature should be maintained at 80°-84° C. by cooling asnecessary. When the additions are completed, the monomer mixture andcatalyst containers and feed lines are rinsed to the kettle with water.The batch is cooled to ambient temperature for storage, or maintained atan appropriate temperature for reaction with the insoluble transitionmetal compound. The resulting polymer has a calculated T_(g) of 43° C.,and a Minimum Filming Temperature (MFT) of 49° C.

MINIMUM FILM FORMING TEMPERATURE

The method of determining minimum film forming temperature (MFT) makesuse of a Minimum Film Forming Temperature Bar, a horizontal, rectangularplate or table which has temperature-measuring thermocouples spaced atregular intervals along its length. By means of heating units locatedwithin the table and a reservoir at one end which can be charged with adry ice/acetone bath, a temperature gradient of 0° to 100° C. ismaintained along the bar. Longitudinal grooves approximately 1/32-inchdeep run the length of the bar and span the complete temperature range.A sample of the polish to be tested is pipeted into one of the grooves,spread along it with the tip of the pipet and allowed to dry. Thetemperature of the bar at the point where the polish residue changesfrom a noncontinuous to a continuous film is noted as the MFT.

EXAMPLE 1 All Acrylic Floor Polish Polymer-Demonstration Of Reaction

A 100 g. sample of uncrosslinked polymer prepared according to the aboveprocedure, with a composition of 28 BA/62 MMA/10 MAA (43° C. T_(g), 49°C. MFT, 43.6% total solids), was heated to 50° C. and 0.62 g. of ZnO(7.60 millimoles; 30% of theoretical stoichiometry based on polymer acidfunctionally) which had been mixed into 15 g of water, was added to thepolymer emulsion in five portions of 3 cc each. Each portion clouded themix, but the cloudiness disappeared within 5 minutes. The emulsionproduct remained free of sediment and had an MFT of 60°-62° C.

The appearance and disappearance of cloudiness after each charge,coupled with the observed increase in MFT of the polymer at the end ofthe procedure and the absence of sediment indicate that the polymer hasreacted with the zinc oxide, yet the polymer retains the ability to forma film when properly formulated.

EXAMPLE 2 Higher Reaction Temperature

The procedure of Example 1 was repeated at 67° C. The disappearance ofcloudiness occurred more rapidly after the addition of each portionindicating a more rapid rate of reaction. The emulsion product remainedfree of sediment, and had an MFT of 58°-60° C.

EXAMPLE 3 Reaction with 40% of Theoretical Stoichiometry of Zinc OxideBased On Polymer Acid Functionality

The procedure of Example 1 was repeated except that the reactiontemperature was 70° C. and the amount of ZnO was 0.83 grams (10.14millimoles; 40% of the theoretical stoichiometry). The mixture cloudedafter addition of each portion of zinc oxide and returned to initialappearance in about 1 minute indicating completion of the reaction andthe system remained free of sediment. The emulsion product had an MFT of69°-71° C.

Comparative A--Below T_(g) of Polymer, No Observed Reaction

To 100 g. of uncrosslinked polymer emulsion with a composition of62MMA/28BA/10MAA (T_(g) of 43° C., MFT of 49° C., 43.6% total solids)was added 1.69 g. of a 49.8% solids ZnO dispersion (10.14 millimoles;40% of theoretical stoichiometry) and 15.24 g. of water. The mixture wasstirred for 1 hour at ambient (22° C.) temperature. However, theincreased opacity of the mixture did not abate, and after standing,heavy sediment developed. The filtered emulsion product had an MFT of48°-50° C., which represents no change in MFT during the aboveprocedure, indicating that no reaction had taken place.

Comparative B--Below T_(g), No Observed Reaction at Lower Stoichiometrywith Stabilized Emulsion to Reduce Sediment

Comparative Experiment A was repeated at 35% of theoretical Znstoichiometry and without heating. Before addition of the ZnOdispersion, the emulsion pH was adjusted to 7.5 with a 10% aqueoussolution of KOH to stabilize the emulsion and to test whether the heavysediment noted in Comparative A was due to polymer precipitation. Afterstirring for 16 hours at room temperature (22° C.), the mixture opacitydid not abate, and after standing, sediment developed. The filteredpolymer emulsion had an MFT of 48°-50° C., which represents no change inMFT during the above procedure, indicating that no reaction had takenplace.

Comparative C--Below T_(g), No Observed Reaction at 30% Stoichiometry

Comparative Experiment B was repeated with ZnO charged at 30% oftheoretical stoichiometry, and sediment again developed. The filteredemulsion product had an MFT of 48°-50° C., indicating that no reactionhad taken place. Analysis of the sediment from this reaction showed itto be Zinc Oxide.

Comparative D--Zinc/amine Complex, Formulated at 50% StoichiometryProduces Sediment

A 100 gram sample of the polymer described in Example 1 was formulatedwith 50% of the theoretical stoichiometry of a zinc/amine complexprepared as described in U.S. Pat. Nos. 3,308,078 and 4,017,662: 50.3grams of Zinc Oxide was reacted with 62.7 grams of Ammonium BiCarbonateand 83.4 grams of 28% Ammonium Hydroxide and diluted with 285 grams ofDI water to form a 1.28 molal solution of Tetra-ammino Zinc BiCarbonate(8.39% Zinc as metal). 9.89 grams of this solution (12.7 millimoles ofZinc) was added over 30 minutes to the rapidly stirring emulsion,maintained at 22° C. After stirring for 6 hours, the mixture was allowedto stand for 16 hours and sediment was observed. This indicates that amixture of 50% stoichiometric amount of zinc/amine complex based onpolymer acid functionality did not form a shelf stable formulation withthis polymer.

EXAMPLE 4 Reaction demonstrated at 50% of Theoretical ZnO Stoichiometry

The experiment of Example 1 was followed except that the emulsionpolymer was maintained at 77° C., and the amount of ZnO was 50% of thetheoretical stoichiometry based on polymer acid functionality (1.03grams, 12.67 millimoles). All of the zinc oxide powder was added in oneshot to the rapidly stirring polymer emulsion. The cloudy reactionmixture returned to a translucent blue appearance in several minutes andthe system remained free of sediment. The resulting emulsion product hadan MFT of 74°-76° C., indicating that a reaction has occurred.

Comparative E--Below T_(g), No Observed Reaction at 50% Theoretical ZnOStoichiometry

The experiment of Example 4 was repeated at 38° C. (below the emulsionpolymer Tg of 43° C.) with 50% of the theoretical stochiometry of ZnO(1.03 grams, 12.67 millimoles). The chalky appearance of the reactionmixture persisted during an hour of stirring at 38° C. and throughout 16hours more of stirring at room temperature (22° C.). After several hoursof standing, a fine white silt settled to the bottom of the reactionmixture. A filtered aliquot of the emulsion product had an MFT of48°-50° C., indicating that reaction had not taken place.

EXAMPLE 5 Heating Unreacted Mixture Above T_(g) Produces Reaction

The product of Comparative Example E (with sediment) was reheated to 77°C. with stirring. The chalky appearance of the reaction mixturedisappeared rapidly. After cooling and standing quiescent for one day,there was no sediment. The emulsion product had an MFT of 74°-76° C.indicating that the reaction occurred.

EXAMPLE 6 Reaction Demonstrated at 60% Theoretical ZnO Stoichiometry

The experiment of Example 4 was repeated with 1.24 grams of ZnO (15.21millimoles; 60% of theoretical stoichiometry), with similar results. Thesediment-free emulsion product had an MFT of 79°-81° C.

EXAMPLE 7 Reaction Demonstrated at 70% Theoretical ZnO Stoichiometry

The experiment of Example 4 was repeated with 1.44 grams of ZnO (17.74millimoles; 70% of theoretical stoichiometry), with similar results. Thesediment-free emulsion product had and MFT of 84°-86° C.

EXAMPLE 8 Reaction Demonstrated at 80% Theoretical ZnO Stoichiometry

The experiment of Example 4 was repeated with 1.65 grams of ZnO (20.28millimoles; 80% of theoretical stoichiometry), with similar results. Thesediment-free emulsion product had an MFT of 88°-90° C.

EXAMPLE 9 Reaction Demonstrated at 90% Theoretical ZnO Stoichiometry

The experiment of Example 4 was repeated with 1.86 grams of ZnO (22.81millimoles; 90% theoretical stoichiometry), with similar results. Thesediment-free emulsion product had an MFT of 91°-94° C.

EXAMPLE 10 Reaction Demonstrated at 100% Theoretical ZnO Stoichiometry

The experiment of Example 4 was repeated with 2.06 grams of ZnO (25.35millimoles; 100% of theoretical stoichiometry). The reaction time, asindicated by the time for development of reduced opacity in the reactionmixture, was more prolonged, and a slight sediment formed on standing.The MFT of the filtered emulsion product was 96°-99° C. whichdemonstrates that reaction occurred to a greater extent than at the 90%stoichiometry of Example 9.

EXAMPLE 11 Reaction Demonstrated at 120% Theoretical ZnO Stoichiometry

The experiment of Example 4 was repeated with 2.48 grams of ZnO (30.42millimoles; 120% of theoretical stoichiometry). In this case, theopacity of the white reaction mixture did not decrease, and asignificant amount of a fine white silt rapidly formed upon standing.The sediment was isolated, washed, analyzed and found to be unreactedZnO. The filtered emulsion product had an MFT of 96°-99° C., indicatingthat the extent of polymer reaction (presumed to be 100% ofstoichiometry) with the ZnO was identical in this experiment with thatof Example 10.

EXAMPLE 12 Floor Polish Vehicle Comparison

A sediment-free sample of emulsion polymer reacted with zinc oxidedispersion to 30% stoichiometry was prepared (product of Example 1). ThepH of this product was adjusted from 6.3 to 7.4 with ammonia, and theemulsion was diluted to 38% total solids with deionized water. The MFTof this emulsion product, Example 12, was 59°-62° C.

Comparative F

An aliquot of the same uncrosslinked starting emulsion as in the aboveexample was crosslinked with 5.99 grams of an 8.3% solution of (NH₃)₄Zn(HCO₃)₂ (the metal salt complex, latent crosslink of the prior art)measured as zinc metal (7.60 millimoles; 30% of theoreticalstoichiometry). The crosslinked emulsion was diluted to 38% total solidswith deionized water. The MFT of this emulsion product, Comparative F,was 60°-62° C.

Floor polishes were prepared from the product of Example 12 andComparative F according to the same basic formulation.

    ______________________________________                                        FORMULATION                                                                                      Parts   Parts                                              ______________________________________                                        Materials                                                                     Polymer F            --        55.92                                          Polymer 12           55.92     --                                             Water                34.71     34.71                                          Abex ® 18S (35%).sup.1                                                                         1.40      1.40                                           FC-129 (1%).sup.2    1.00      1.00                                           SWS-211.sup.3        0.02      0.02                                           Diethylene glycol monomethyl ether                                                                 3.30      3.30                                           Dipropylene glycol methyl ether                                                                    5.00      5.00                                           Tributoxy ethyl phosphate                                                                          1.70      1.70                                           Dibutyl Phthalate    1.70      1.70                                           Formalin (37%)       0.15      0.15                                           POLY-EM ® 40 (40%).sup.4                                                                       9.37      9.37                                           Formulation Constants                                                         Polymer/ASR/Wax ratio.sup.5                                                                        85/0/15   85/0/15                                        Theoretical non-volatile solids                                                                    25.4%     25.4%                                          pH                   7.2       8.5                                            ______________________________________                                         .sup.1 A product of Alcolac, Inc.                                             .sup.2 A product of 3M Company                                                .sup.3 A product of Wacker Silicone Corporation                               .sup.4 A product of Rohm and Haas Company                                     .sup.5 ASR = Alkali soluble resin                                        

The two polishes were applied to vinyl floor tiles' and vinyl compositefloor tiles and tested according to the indicated test procedures. Inthe tables below "vinyl" indicates a test applied to solid vinyl tileand "VCT" indicates a test applied to vinyl composition tile. Thefollowing comparisons were noted:

In the tables the following abbreviations have the meanings indicated:G=good, VG=very good; Ex or Exc=Excellent; a hyphenated rating such asG-VG indicates the performance was rated as between the two scores.

    __________________________________________________________________________                            Polish Basis Polymer                                                          Example 12                                                                             Comparative F                                __________________________________________________________________________    GLOSS (ASTM D 1455):                                                          1st coat vinyl          VG       G-VG                                         2nd coat vinyl          VG-EX    VG-EX                                        1st coat VCT            G        G                                            2nd coat VCT            VG-EX    VG-EX                                        LEVELING (ASTM D 3153):                                                       1st coat vinyl          G-VG     G-VG                                         2nd coat vinyl          VG       VG                                           WATER RESISTANCE (ASTM D 1793):                                               1 hour vinyl/VCT        G-VG/VG  G-VG/VG                                      24 hour vinyl/VCT       VG/VG-EX VG/VG-EX                                     DETERGENT RESISTANCE (ASTM D 3207)                                            1/20 dilution of Forward ® in water):                                     1 day (vinyl/VCT)       VG-EX/VG-EX                                                                            VG-EX/VG-EX                                  7 day (vinyl/VCT)       EX/EX    EX/EX                                        REMOVABILITY (ASTM D 1792):                                                   1/20 dilution of Forward ®, with 1% Ammonia)                              7 day vinyl/VCT         G/EX     G/EX                                         RECOATABILITY (ASTM 3153):                                                                            Exc*     Exc*                                         STRESS RECOATABILITY (modified ASTM                                           3153, with 20 minute recoat time):                                            REDISPERSION            Exc      Fair                                         DRAG                    Exc      Fair                                         WHITENING               Exc      Fair                                         GHOSTING                Exc      Good                                         __________________________________________________________________________     *A combined rating for all parameters = Excellent                        

The above data demonstrate that the polymer emulsion of Example 12matched the positive performance properties of latent metal saltcrosslinking without the recoat problems shown by the data forComparative F reported under Stress Recoatability.

The Stress Recoatability data provides a more rigorous test ofrecoatability than the standard ASTM test; a second coat of polish isapplied after an interval of 20 minutes to examine the performance ofthe polish emulsion if a second coat were applied in less than therecommended one hour interval, as does occur when the user attempts torapidly build up a multicoat finish. Under this more rigorous challengethe polish prepared from the polymer of Example 12 exhibited `excellent`performance on all test parameters. In contrast, the Comparative Fpolish exhibited `fair` performance on the redispersion, applicator dragand whitening tests and `good` on the ghosting test. This translatesinto more difficult spreading (applicator drag) and a diminishedappearance quality (whitening, redispersion and ghosting) forComparative F polish.

EXAMPLE 13 Styrenated Floor Polish Vehicle

A polymer was prepared according to Procedure A above, from a monomermixture of 52 parts methyl methacrylate/28 parts butyl acrylate/12 partsstyrene/8 parts methacrylic acid (calculated Tg of 48° C., and empericalMFT of 54°-55° C.).

To 100 g of the above uncrosslinked styrenated emulsion polymer (44.0%solids) at 65° C. was added 0.58 g (7.61 millimoles) of powdered ZnO(Kadox 515) and 14.42 g of H₂ O. This corresponds to 35% of thetheoretical stoichiometry of Zinc, based on the polymeric acid content.The white ZnO powder reacted slowly, and the sample was free ofsediment. The emulsion polymer product had an MFT of 65°-66° C.

EXAMPLE 14 Dispersion of ZnO Increases Reaction Rate

The experiment of Example 13 was repeated, but instead of powdered ZnO,1.17 grams (7.61 millimoles; 35% of theoretical stoichiometry) of a49.8% ZnO solids dispersion (0.1% Tamol 731 dispersant and Dl water) wasemployed. The mixture became white and opaque but returned to initialappearance rapidly with stirring and the product was free of sedimentafter standing. The emulsion polymer product had an MFT of 65°-67° C.

Comparative G Styrenated Floor Polish with Metal Complex

The polymer emulsion of Example 13 was treated with 7.81 grams of a Zinccomplex solution formed from 46.7 grams ZnO, 110 grams NH₄ OH (28%),68.7 grams NH₄ HCO₃, 37.5 grams Dimethylamino ethanol, and diluted withwater to 5.99% Zn (as a metal). The theoretical stoichiometry of the Znwas 35%, based on polymeric acid. The emulsion polymer product had anMFT of 63°-64° C.

The emulsion products of Example 14 and Comparative G were formulatedand tested as floor polish vehicles.

    ______________________________________                                        Formulation for Styrenated Acrylic Floor Polish                                                 Ex. 14    Comparative G                                     POLISH            Parts     Parts                                             ______________________________________                                        Materials                                                                     Water             37.78     37.78                                             Acrysol ® 644 (42%).sup.1                                                                   5.96      5.96                                              FC-120 (1%)       0.75      0.75                                              SWS-211           0.02      0.02                                              Diethylene glycol monethyl ether                                                                6.67      6.67                                              Tributoxethyl phosphate                                                                         1.67      1.67                                              Formalin (37%)    0.15      0.15                                              Polymer 14        46.88     --                                                Comparative G     --        46.88                                             Poly-Em (40 (40%) 9.30      9.30                                              Formulation Constants                                                         Polymer/ASR/Wax ratio                                                                           75/10/15  75/10/15                                          Theoretic non-volatile solids                                                                    24.5%     24.5%                                            pH                7.4       8.9                                               Viscosity (Brookfield LVT,                                                                      6.6       8.0                                               ultra-low adapter, 60 rpm.)                                                   ______________________________________                                         .sup.1 A product of Rohm and Haas Company, neutralized to pH 7.5 with         NH.sub.4 OH after addition.                                              

    ______________________________________                                                       Example 14  Comparative G                                      Test Results   Metal Oxide Metal Complex                                      ______________________________________                                        Gloss (v/vct)  VG-EXC/VG   VG-EXC/VG                                          Leveling       VG-EXC      VG-EXC                                             Recoatability  EXC         G-VG                                               Water resist   VG          VG                                                 Detergent resist                                                                             EXC         G-VG                                               Removability   GOOD        GOOD                                               Stress Recoatability                                                          Redispersion   EXC         GOOD                                               Drag           EXC         GOOD                                               Whitening      EXC         GOOD                                               Ghosting       EXC         GOOD                                               ______________________________________                                    

The polymer of Example 14 exhibited better stress recoat performancethan Comparative G.

EXAMPLE 15

A styrenated acrylic emulsion polymer was prepared according toprocedure A above, from a monomer mixture of 34 parts methylmethacrylate/28 parts butyl acrylate/25 parts styrene/5 partsacrylonitrile/8 parts methacrylic acid (calculated Tg of 47° C., andemperical MFT of 54°-55° C.).

This polymer was reacted with 95% of theoretical stoichiometry of Zincoxide at 65° C. The reaction mixture turned opaque then returned toinitial appearance and no sediment was observed. The emulsion polymerproduct had an MFT of 70° C.

After the emulsion pH was adjusted from 5.8 to 7.3 with ammonia (MFT of68° C.), the polymer was formulated into a floor polish with goodperformance properties and excellent stress recoatability.

EXAMPLE 16 High Glass Transition Temperature Polymer

A polymer was prepared according to Procedure A from a monomer mixtureof 59 parts styrene, 21 parts butyl acrylate and 20 parts methacrylicacid. The 40.6% solids emulsion, with a calculated T_(g) of 62° C., hada pH of 5.1 and an MFT of 68°-70° C. The emulsion was heated to 70°-72°C. and charged with 10.66 grams (47.2 millimoles; 50% of theoreticalstoichiometry based on polymeric acid) of a Zn(OH)₂ dispersion made from44 grams of powdered Zinc Hydroxide in 56 grams of a 0.75% solution ofTamol 731 dispersant in water (28.95% Zn as metal). After about onehour, the reaction mixture was noted to have become less opaque and hadreturned to its original appearance. The reaction product was free ofsediment and had an MFT of 96° C., and a pH of 6.2. All three of theseproperties are indications that a reaction had taken place between thepolymer and the insoluble transition metal compound.

SEQUENTIALLY POLYMERIZED FLOOR POLISH VEHICLE Procedure B Monomermixture preparation

Two monomer emulsion mixtures (M.E.#1 and M.E.#2) were prepared byadding the following monomers slowly and in sequence to a stirredsolution of 6.3 parts of a 28% solution of Sodium Lauryl Sulfate in 858parts of deionized water:

    ______________________________________                                                          Monomer Emulsion                                                                #1      #2                                                Monomer             Parts   Parts                                             ______________________________________                                        butyl acrylate      537     --                                                methyl methacrylate 187.5   88.5                                              hydroxyethyl methacrylate                                                                          88.5   --                                                styrene             --      715.5                                             methacrylic acid    81      --                                                acrylic acid        --      88.5                                              ______________________________________                                    

Polymerization

In a suitable reaction vessel equipped with a thermometer, condensor,and stirrer, a solution of 51 parts of 28% SLS solution and 858 partsdeionized water is heated to 80°-85° C. 51 parts of monomer emulsion #1described above is added all at once to the reaction vessel and thetemperature will drop to 80°-82° C. A kettle charge ammonium persulfate(APS) catalyst solution (8.4 parts dissolved in 48 parts water) is addedall at once. Within about five minutes the onset of polymerization issignalled by a temperature rise of 3°-5° C. and a change in theappearance (color and opacity) of the reaction mixture. When theexotherm has ceased, the remaining monomer emulsion #1 and the cofeedcatalyst solution (1.2 parts APS in 64.5 parts deionized water) aregradually added to the reaction vessel. The rate of addition must bechosen based on the rate at which the heat of the polymerizationreaction can be removed by cooling (1- 2 hrs). The polymerizationreaction temperature should be maintained at 80°-88° C. by cooling asnecessary. When the additions are completed, the monomer emulsion #1 andcatalyst containers and feed lines are rinsed to the kettle with 30parts water. The reaction mixture is held at 82°-86° C. for 15 minutes,and then the monomer emulsion #2 and the cofeed catalyst solution (1.2parts APS in 64.5 parts deionized water) are gradually added to thereaction vessel. The rate of addition must be chosen based on the rateat which the heat of the polymerization reaction can be removed bycooling (1-2 hrs). The polymerization reaction temperature should bemaintained at 80°-88° C. by cooling as necessary. When the additions arecompleted, the monomer emulsion #2 and catalyst containers and feedlines are rinsed to the kettle with 30 parts water. After holding thereaction mixture at 83°-88° C. for 15 minutes, a chase solution of 1.3parts t-Butyl HydroPeroxide in 9 parts water is added in 10 minutes andthen a second chase of 0.5 parts iso-Ascorbic Acid in 39 parts water isadded over 15 minutes. During this latter addition, no external heatingis applied to the vessel. The batch is cooled to ambient temperature forstorage, or maintained at an appropriate temperature for reaction withthe insoluble transition metal compound. The resulting polymer has anemperical T_(g) of 10° C. (first sequential polymer), 110° C. (secondsequential polymer), and an effective (overall) T_(g) of 55° C. The46.9% solids emulsion, with a composition of 30 BA/10.5 MMA/5 HEMA/4.5MAA/40 Styrene/5 MMA/5 AA, has a Minimum Filming Temperature (MFT) of32° C.

EXAMPLE 17

100 grams of uncrosslinked emulsion sequential polymer preparedaccording to the above procedure was heated to 60° C. and 1.39 grams ofZnO (17.13 millimoles; 60% of theoretical stochiometry, based on totalpolymeric acid functionality), dispersed in 10 grams of water, was addedwith stirring. After 20 minutes it was noted that the very chalkyappearance of the reaction mixture had returned to the milky appearanceof the initial emulsion. On cooling, and after standing over night itwas noted that a soft, slightly gellatinous sediment had formed.

This sediment was analyzed and found to be identical in composition andpolymer/Zinc ratio to the supernatant emulsion solids, and alsoidentical to the theoretical composition and polymer/metal ratio of thereaction mixture. The reaction product emulsion, however, is apparentlynot stable, forming the sediment as a result of mechanical, chemical, orthermal shock encountered in the reaction process. The filtered emulsionhad an MFT of 44° C., indicating that reaction with the metal salt hastaken place.

EXAMPLE 18

The experiment of Example 17 was repeated, but before the ZnO dispersionwas added the pH 4.8 polymer emulsion was partially neutralized with 10%Potassium Hydroxide solution to pH 6 in order to improve the mechanicaland chemical stability of the emulsion. After reaction with the metalcompound, the sediment-free emulsion had an MFT of 46°-48° C., and itwas stable to freeze/thaw cycling (3 cycles, ASTM D 3209) and 3 minutesWaring Blender mechanical stability testing.

The reaction product emulsion pH was adjusted to 7.2 (MFT 44°-45° C.)with ammonia before formulating it as a floor polish.

EXAMPLE 19

The experiment of Example 17 was repeated, but before the ZnO dispersionwas added the pH 4.8 polymer emulsion was partially neutralized with 5%Ammonium Hydroxide solution to pH 6. After reaction with the metal salt,the sediment-free emulsion had an MFT of 44°-47° C., and it was stableto freeze/thaw cycling (3 cycles, ASTM D 3209) and 3 minutes WaringBlender mechanical stability testing.

Comparative H

The uncrosslinked sequential polymer emulsion of Examples 17-19 wascrosslinked to 60% stochiometry with a (NH₃)₄ Zn(HCO₃)₂ solutionprepared by mixing 100 g. DI H₂ O, 66 g NH₄ HCO₃, 139 g. NH₄ OH(28%), 59g. ZnO. The metal complex solution, after clarifying, was diluted to8.3% Zn (as metal) and 13.49 grams was slowly added to 100 grams of thestirring emulsion polymer at 30° C. No sediment or gel formed. The pH9.2 product emulsion had an MFT of 42°-44° C., and was both mechanicaland freeze/thaw stable.

Data for Example 18 and Comparative H polish formulations is presented.

    ______________________________________                                        FORMULATION:                                                                  ______________________________________                                                           Ex. 18    Comp. H                                                             PARTS     PARTS                                            ______________________________________                                        MATERIAL IN                                                                   ORDER OF ADDITION                                                             Water              52.64     52.64                                            Acrysol 644 (42%)  1.29      1.29                                             FC-120 (1%)        0.43      0.43                                             SWS-211            0.014     0.014                                            Dipropylene Glycol Methyl Ether                                                                  4.40      4.40                                             Tributoxy Ethyl Phosphate                                                                        0.82      0.82                                             Formalin (37%)*    0.15      0.15                                             Ex 17 Polymer      38.84     --                                               Comparative H Polymer                                                                            --        38.80                                            Poly-Em 40 (40%)   3.38      3.38                                             A-C 325N (35%)     3.85      3.85                                             FORMULATION CONSTANTS                                                         Polymer/ASR/Wax Ratio                                                                            82/3/15   82/3/15                                          Theoretical Non-Volatile Solids                                                                  17.8%     17.8%                                            pH                 7.3       9.2                                              ______________________________________                                                           Example 18                                                                              Comparative H                                    ______________________________________                                        TEST RESULTS                                                                  Recoatability      EX        EX                                               Stress Recoatability                                                          redispersion       Exc       Good                                             drag               Exc       Exc                                              whitening          Exc       Fair                                             Ghosting           Exc       Good                                             ______________________________________                                    

All other polish performance properties were essentially equal.

Solubilized Low Molecular Weight Floor Polish

All of the previous examples have been with high (≧2.5 million)molecular weight polymers. The technology can also be applied to lowermolecular weight acid-containing polymers, such as those preparedaccording to U.S. Pat. No. 4,017,662. These polymers are intended to beaqueous base solubilized, so if the stoichiometric level of the metalcompound exceeds a certain point the polymer will be destabilized andwill no longer be soluble in the alkaline aqueous medium (This pointvaries with the molecular weight and acid content of the polymer).

A polymer emulsion was prepared according to Procedure A above, from amonomer mixture of 52.5 MMA/ 29.5 BA/ 18 MAA, and with 1.5% by weight,based on total monomers, 3-Mercapto Propionic Acid (3-MPA) as a chaintransfer agent. The resulting polymer, with a measured T_(g) of 81° C.(Differential Scanning Colorimetry) molecular weight (M_(w)) of 32,700and a number averaged molecular weight (M_(n)) of 13,500, with anintrinsic viscosity (THF at 30° C.) of 0.13. As prepared at pH 5.4, the39% solids emulsion has an MFT of 84° C., but the polymer is solubilized(optical transmission ≧97% at 525 nm) when the pH is adjusted to greaterthan 6.7 with Ammonium Hydroxide solution. The MFT of the solubilizedpolymer, measured at pH 7.5, was found to be less than room temperature(22° C.).

EXAMPLE 20

A 100 gram aliquot of the un-neutralized 39% total solids polymeremulsion described above was reacted with 0.80 grams of a 49.4% Zn(OH)₂dispersion (3.98 millimoles; 10% theoretical stoichiometry) at 85° C.The emulsion polymer product had an MFT of 90° C., and was solubilized(optical transmission of 95% at 525 nm) when the pH was adjusted to 7.4with ammonia (MFT 30° C.). The solubilized polymer had an MFT of 26° C.at pH 7.8.

EXAMPLE 21 High Acid Copolymer

A polymer emulsion was prepared according to Procedure A, with acomposition of 35 Ethyl Acrylate/65 Methacrylic Acid. It was necessaryto increase the level of primary emulsifier (SLS) in both the monomeremulsion and the kettle charge to twice that of the polymer of Example 1in order to limit the amount of aqueous phase initiatedhomopoly(methacrylic acid). The resulting polymer emulsion (calculatedTg of 80° C.), at 20.2% solids, had a pH of 3.5 and an MFT of 83°-85° C.When basified to pH 5.8 with a few drops of a 10% solution of PotassiumBiCarbonate, the MFT dropped to 55°-60° C.

The above emulsion polymer as basified to pH 5.8, was reacted at 85° C.with a dispersion of ZnO prepared from 73.4 grams water, 1.6 grams Tamol960 dispersant, and 25 grams ZnO (Kadox 515). A 9.84 grams sample ofthis ZnO dispersion (30.3 millimoles; 39.6% of theoretical stochiometry)was added to 100 grams of the emulsion in one shot. The very chalkyappearance of the reaction mixture was noted to rapidly revert to thetranslucent blue appearance of the original emulsion. No sedimentformed, and the reaction product had an MFT greater than 100° C.

EXAMPLE 22 Use of Copper Demonstrated

To 100 grams of a sample of polymer prepared according to the procedureA above with a composition of 28 BA/62 MMA/10 MAA (43° C. T_(g), 48° C.MFT, 43.6% total solids), was added 1.01 grams of black Cupric Oxidepowder (12.66 millimoles; 50% of theoretical stochiometry based onpolymeric acid functionality). After reaction at 65° C., thissediment-free mixture yielded a lightly colored blue-green emulsion withan MFT of 75° C. The increasd MFT indicates that reaction with thepolymer occured. This emulsion was basified to pH 7.2 with PotassiumBiCarbonate and formulated into a polish that exhibited acceptibleperformance properties.

EXAMPLE 23 Use of Nickel Demonstrated

To 100 grams of a sample of polymer prepared according to the procedureA above with a composition of 28 BA/62 MMA/10 MAA (43° C. T_(g), 49° C.MFT, 43.6% total solids), was added 1.17 grams of green Nickle Hydroxide(Ni(OH)₂) powder (12.65 millimoles; 50% of theoretical stochiometrybased on polymeric acid functionality). After reaction at 65° C., thissediment-free mixture yielded a light pink emulsion with an MFT of78°-80° C. The increasd MFT indicates that reaction with the polymeroccured. This emulsion was basified to pH 7.2 with Potassium BiCarbonateand formulated into a polish that exhibited acceptible performanceproperties.

EXAMPLE 24 Industrial Coatings Vehicle

A polymer was prepared according to procedure A above, having acomposition of 38.3 Hexyl methacrylate, 30.1 Styrene, 24.7 Acrylonitrile6.9 Methacrylic Acid (T_(g) =58° C. ) and placed in a reaction vessel.An aqueous mixture containing 0.98 g ZnO (12.04 millimoles; 30%stoichiometric equivalent based on Zn as metal), and 1.66 g K₂ CO₃ (12milliequivalents) was added. The temperature of the reaction vessel was65° C. After the reaction 1.35 g KOH (24 millimoles) were added. Thereaction product was formulated into standard 15 PVC white enamel andapplied to a steel substrate and baked. The resulting film exhibitedimproved performance versus a film containing the same polymer withoutcrosslinking, and versus a film of uncrosslinked polymer having a T_(g)of 60° C., when tested for early print and block resistance, solventresistance (MEK rub), direct and reverse impact hardness. Thisdemonstrates that the products of the invention are useful in industrialcoatings on metals and other substrates such as plastic and wood.

We claim:
 1. A composition comprising the product of the reaction in anaqueous system of:(a) the pendant acid functionality of a polymerprepared from more than one ethylenically unsaturated monomer, includingfrom about 4 to about 90 weight percent of acid-functional monomer(s),said polymer having a calculated T_(g) of from greater than about roomtemperature to less than the decomposition temperature of the polymer,with (b) a transition metal compound, at a temperature about thecalculated T_(g) of said polymer and below the decomposition temperatureof said polymer; for a time sufficient to produce a degree of reactionof said acid and metal indicated by the product having a minimum filmingtemperature above that of said polymer prior to the reaction; andwherein said reaction product is capable of forming a film.
 2. Thecomposition of claim 1, wherein the transition metal is selected fromthe group consisting of zinc, aluminum, tin,. tungsten and zirconium. 3.The composition of claim 1, wherein the transition metal compound is anoxide, hydroxide carbonate or acetate.
 4. The composition of claim 1,wherein the amount of transition metal compound is from about 10 toabout 100 percent of the stoichiometric amount based on polymer acidfunctionality.
 5. The composition of claim 1 further comprisingpigments, fillers wetting, emulsifying and dispersing agents.
 6. A floorpolish composition comprising:(a) the composition of claim 1; (b) analkali-soluble resin; (c) a wax; (d) a wetting agent; (e) an emulsifyingagent; (f) a dispersing agent; and (g) water in an amount to make thetotal solids of the composition from about 2 to about 55 percent.
 7. Thecomposition of claim 1, wherein the polymer is an aqueous emulsion ordispersion and the transition metal compound is insoluble in water.